Method for preparing precipitated silicas, novel precipitated silicas and their uses, in particular for strengthening polymers

ABSTRACT

The invention relates to a novel process for the preparation of a precipitated silica, in which:
         a silicate is reacted with an acidifying agent, so as to obtain a suspension of precipitated silica,   said suspension of precipitated silica is filtered, so as to obtain a filtration cake,   said filtration cake is subjected to a liquefaction operation comprising the addition of an aluminum compound,   after the liquefaction operation, a drying stage is carried out, characterized in that a polycarboxylic acid chosen from dicarboxylic acids and tricarboxylic acids is added to the filtration cake after the addition of the aluminum compound.       

     It also relates to novel precipitated silicas and to their uses.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national phase entry under 35 U.S.C. § 371 ofInternational Application No. PCT/EP2013/068108, filed on Sep. 2, 2013,which claims priority to French Application No. 12 02350, filed on Aug.31, 2012. The entire contents of these applications are explicitlyincorporated herein by this reference.

The present invention relates to a novel process for the preparation ofprecipitated silica, to novel precipitated silicas and to theirapplications, such as the reinforcement of polymers.

It is known to employ reinforcing white fillers in polymers, inparticular elastomers, such as, for example, precipitated silica.

The aim of the present invention is to provide in particular analternative filler for polymer compositions which advantageouslyprovides them with a reduction in their viscosity and an improvement intheir dynamic properties, while retaining their mechanical properties.It thus advantageously makes possible an improvement in thehysteresis/reinforcement compromise.

The present invention first of all provides a novel process for thepreparation of precipitated silica employing, during or after theliquefaction operation, a particular polycarboxylic acid.

Generally, the preparation of precipitated silica is carried out by aprecipitation reaction of a silicate, such as an alkali metal silicate(for example sodium silicate), with an acidifying agent (for examplesulfuric acid), then separation by filtration, with a filtration cakebeing obtained, of the precipitated silica obtained, subsequentlyliquefaction said filtration cake and, finally, drying (generally byatomization). The silica can be precipitated in any mode: in particular,addition of acidifying agent to a silicate vessel heel or total orpartial simultaneous addition of acidifying agent and of silicate to avessel heel of water or of silicate.

The subject matter of the invention is a novel process for thepreparation of a precipitated silica, in which:

at least one silicate is reacted with at least one acidifying agent, soas to obtain a suspension of precipitated silica,

the suspension of precipitated silica obtained is filtered, so as toobtain a filtration cake,

the filtration cake obtained on conclusion of the filtration issubjected to a liquefaction operation comprising the addition of analuminum compound,

after the liquefaction operation, a drying stage is preferably carriedout (generally by atomization),

characterized in that a polycarboxylic acid chosen from dicarboxylicacids and tricarboxylic acids is added to the filtration cake after theaddition of the aluminum compound.

According to the invention, the polycarboxylic acid (advantageouslysuccinic acid) is preferably used without supplementary addition ofanother (poly)carboxylic acid.

The liquefaction operation is a fluidification or liquefactionoperation, in which the filtration cake is rendered liquid, theprecipitated silica being re-encountered in suspension.

In the invention, this operation is carried out by subjecting thefiltration cake to a chemical action by addition of an aluminumcompound, for example sodium aluminate, preferably coupled with amechanical action (for example, by passing through a continuouslystirred tank or through a mill of colloid type) which normally bringsabout a reduction in particle size of the suspended silica.

In a first alternative form, during the liquefaction operation, thealuminum compound is added to the filtration cake prior to the additionof the polycarboxylic acid (advantageously succinic acid).

In a second (preferred) alternative form, the polycarboxylic acid(advantageously succinic acid) is added after the liquefactionoperation, that is to say, to the disintegrated filtration cake.

The mixture then obtained (suspension of precipitated silica) issubsequently dried (generally by atomization).

The filtration cake which has to be subjected to the liquefactionoperation can be composed of the mixture of several filtration cakes,each of said cakes being obtained by filtration of a portion of thesuspension of precipitated silica obtained above.

Advantageously, the polycarboxylic acid used in the process according tothe invention is succinic acid.

The polycarboxylic acid (advantageously succinic acid) employedaccording to the invention can be in the anhydride, ester, alkali metal(for example sodium or potassium) salt (carboxylate) or ammonium salt(carboxylate) form.

The polycarboxylic acid (advantageously succinic acid) used in theinvention can optionally be preneutralized (in particular by pretreatingit with a base, for example of sodium hydroxide or potassium hydroxidetype) before it is added to the filtration cake. This makes it possiblein particular to modify the pH of the silica obtained.

The polycarboxylic acid, advantageously succinic acid, can be employedin the form of an aqueous solution.

Preferably, the aluminum compound is chosen from alkali metalaluminates. In particular, the aluminum compound is sodium aluminate.

According to the invention, the amount of aluminum compound (inparticular sodium aluminate) used is generally such that the ratio ofaluminum compound to amount of silica, expressed as SiO₂, present in thefiltration cake is between 0.20% and 0.50% by weight, preferably between0.25% and 0.45% by weight.

The amount of polycarboxylic acid employed is in general such that theratio of polycarboxylic acid to amount of silica, expressed as SiO₂,present in the filtration cake (at the time of the addition of thepolycarboxylic acid) is between 0.75% and 2% by weight, preferablybetween 1% and 1.75% by weight, in particular between 1.1% and 1.5% byweight.

In the invention, the filtration cake can optionally be washed.

The precipitated silica thus obtained after the addition of thepolycarboxylic acid (advantageously succinic acid) to the silicasuspension obtained after the liquefaction operation is subsequentlydried. This drying operation can be carried out by any means known perse.

Preferably, the drying operation is carried out by atomization. To thisend, use may be made of any type of suitable atomizer, in particular arotary, nozzle, liquid pressure or two-fluid atomizer. In general, whenthe filtration is carried out using a filter press, a nozzle atomizer isused and, when the filtration is carried out using a vacuum filter, arotary atomizer is used.

When the drying operation is carried out using a nozzle atomizer, theprecipitated silica capable of then being obtained usually exists in theform of substantially spherical beads.

On conclusion of this drying operation, it is optionally possible tocarry out a stage of milling the product recovered; the precipitatedsilica capable of then being obtained generally exists in the form of apowder.

When the drying operation is carried out using a rotary atomizer, thesilica capable of then being obtained can exist in the form of a powder.

Finally, the product, dried (in particular by a rotary atomizer) ormilled as indicated above, can optionally be subjected to anagglomeration stage which comprises, for example, a direct compression,a wet granulation (that is to say, with the use of a binder, such aswater, silica suspension, and the like), an extrusion or, preferably, adry compacting. When the latter technique is employed, it can prove tobe opportune, before carrying out the compacting, to deaerate (operationalso referred to as predensifying or degassing) the pulverulent productsso as to remove the air included in the latter and to provide moreuniform compacting.

The precipitated silica capable of then being obtained by thisagglomeration stage generally exists in the form of granules.

Another subject matter of the present invention is a specific processfor the preparation of a precipitated silica of the type comprising theprecipitation reaction between a silicate and an acidifying agent,whereby a suspension of precipitated silica is obtained, followed by theseparation and the drying of this suspension, characterized in that itcomprises the following successive stages:

the precipitation reaction is carried out in the following way:

-   -   (i) an initial vessel heel comprising at least a portion of the        total amount of the silicate involved in the reaction and an        electrolyte is formed, the concentration of silicate (expressed        as SiO₂) in said initial vessel heel being less than 100 g/l        and, preferably, the concentration of electrolyte in said        initial vessel heel being less than 19 g/l,    -   (ii) the acidifying agent is added to said vessel heel until a        pH value for the reaction medium of at least 7.0, in particular        of between 7 and 8.5, is obtained,    -   (iii) acidifying agent and, if appropriate, simultaneously the        remaining amount of silicate is/are added to the reaction        medium,

the silica suspension obtained is filtered,

the filtration cake obtained on conclusion of the filtration issubjected to a liquefaction operation comprising the addition of analuminum compound,

the filtration cake thus obtained, preferably exhibiting a solidscontent of at most 25% by weight, is dried,

said process being characterized in that a polycarboxylic acid chosenfrom dicarboxylic acids and tricarboxylic acids is added to thefiltration cake, either during the liquefaction operation after theaddition of the aluminum compound, or after the liquefaction operationand before the drying stage.

Advantageously, the polycarboxylic acid is succinic acid.

That which is indicated in the above account on the subject of theliquefaction operation, of the addition of the polycarboxylic acid andof the two alternative forms of the process applies to the presentprocess according to the invention.

The choice of the acidifying agent and of the silicate is made in a waywell known per se.

Use is generally made, as acidifying agent, of a strong inorganic acid,such as sulfuric acid, nitric acid or hydrochloric acid, or also of anorganic acid, such as acetic acid, formic acid or carbonic acid.

The acidifying agent can be dilute or concentrated; its normality can bebetween 0.4 and 36N, for example between 0.6 and 1.5N.

In particular, in the case where the acidifying agent is sulfuric acid,its concentration can be between 40 and 180 g/l, for example between 60and 130 g/l.

Use may be made, as silicate, of any common form of silicates, such asmetasilicates, disilicates and advantageously an alkali metal silicate,in particular sodium or potassium silicate.

The silicate can exhibit a concentration (expressed as SiO₂) of between40 and 330 g/l, for example between 60 and 300 g/l.

Preferably, use is made, as silicate, of sodium silicate.

In the case where use is made of sodium silicate, the latter generallyexhibits an SiO₂/Na₂O ratio by weight of between 2 and 4, in particularbetween 2.4 and 3.9, for example between 3.1 and 3.8.

During stage (i), a vessel heel is formed which comprises silicate andan electrolyte. The amount of silicate present in the initial vesselheel advantageously represents only a portion of the total amount ofsilicate involved in the reaction.

As regards the electrolyte present in the initial vessel heel (stage(i)), this term is understood here as normally accepted, that is to saythat it means any ionic or molecular substance which, when it is insolution, decomposes or dissociates to form ions or charged particles;mention may be made, as electrolyte, of a salt of the group of thealkali metals and alkaline earth metals, in particular the salt of thestarting silicate metal and of the acidifying agent, for example sodiumchloride in the case of the reaction of a sodium silicate withhydrochloric acid or, preferably, sodium sulfate in the case of thereaction of a sodium silicate with sulfuric acid.

According to one characteristic of this preparation process, theconcentration of electrolyte in the initial vessel heel is less than 19g/l, in particular less than 18 g/l, especially less than 17 g/l, forexample less than 15 g/l (while generally being greater than 6 g/l).

According to another characteristic of this process, the concentrationof silicate (expressed as SiO₂) in the initial vessel heel is less than100 g/l. Preferably, this concentration is less than 80 g/l, inparticular than 70 g/l. In particular, when the acid used for theneutralization exhibits a high concentration, in particular of greaterthan 70%, it is then advisable to work with an initial vessel heel ofsilicate, the SiO₂ concentration of which is less than 80 g/l.

The addition of acidifying agent in stage (ii) leads to a correlatingfall in the pH of the reaction medium and is carried out until a valuefor the pH of the reaction medium of at least 7, in particular ofbetween 7 and 8.5, for example of between 7.5 and 8.5, is reached.

Once the desired pH value has been reached, and in the case of astarting vessel heel comprising only a portion of the total amount ofthe silicate involved, a simultaneous addition of acidifying agent andof the remaining amount of silicate is then advantageously carried outin stage (iii).

This simultaneous addition is generally carried out in such a way thatthe value of the pH of the reaction medium is always equal (to within±0.1) to that reached on conclusion of stage (ii).

On conclusion of stage (iii) and in particular after the abovementionedsimultaneous addition, a maturing of the reaction medium (aqueoussuspension) obtained can be carried out, at the pH obtained onconclusion of stage (iii), in general with stirring, for example for 2to 45 minutes, in particular for 3 to 30 minutes.

Finally, it is possible, both in the case of a starting vessel heelcomprising only a portion of the total amount of silicate involved andin the case of a starting vessel heel comprising the total amount ofsilicate involved, after the precipitation, in an optional subsequentstage, to add an additional amount of acidifying agent to the reactionmedium. This addition is generally carried out until a pH value ofbetween 3 and 6.5, preferably between 4 and 6.5, is obtained.

The temperature of the reaction medium is generally between 75 and 97°C., preferably between 80 and 96° C.

According to an alternative form of this preparation process, thereaction is carried out at a constant temperature of between 75 and 97°C. According to another alternative form of this process, thetemperature at the end of the reaction is higher than the temperature atthe start of the reaction: thus, the temperature at the start of thereaction is preferably maintained between 75 and 90° C.; then, thetemperature is increased in a few minutes, preferably up to a value ofbetween 90 and 97° C., at which it is maintained until the end of thereaction.

On conclusion of the stages which have just been described, a silicaslurry is obtained, which slurry is subsequently separated (liquid/solidseparation). This separation normally comprises a filtration, followed,if necessary, by a washing operation, carried out by means of anysuitable method, for example by means of a belt filter, a vacuum filteror, preferably, a filter press.

The filtration cake is then subjected to a liquefaction operationcomprising the addition of an aluminum compound.

In accordance with the above account, succinic acid is added, during theliquefaction operation after the addition of the aluminum compound orafter the liquefaction operation and before the drying stage, to thedisintegrated filtration cake. According to the preferred alternativeform, the succinic acid is added after the liquefaction operation to thedisintegrated filtration cake.

The filtration cake thus obtained is subsequently dried.

Preferably, in this preparation process, the suspension of precipitatedsilica obtained after the liquefaction operation should exhibit,immediately before it is dried, a solids content of at most 25% byweight, in particular of at most 24% by weight, especially of at most23% by weight, for example of at most 22% by weight.

This drying operation can be carried out according to any means knownper se. Preferably, the drying operation is carried out by atomization.To this end, use may be made of any type of suitable atomizer, inparticular a rotary, nozzle, liquid pressure or two-fluid atomizer. Ingeneral, when the filtration is carried out using a filter press, anozzle atomizer is used and, when the filtration is carried out using avacuum filter, a rotary atomizer is used.

When the drying operation is carried out using a nozzle atomizer, theprecipitated silica capable of then being obtained usually exists in theform of substantially spherical beads. On conclusion of this dryingoperation, it is optionally possible to carry out a stage of milling theproduct recovered; the precipitated silica capable of then beingobtained generally exists in the form of a powder.

When the drying operation is carried out using a rotary atomizer, theprecipitated silica capable of then being obtained can exist in the formof a powder.

Finally, the dried (in particular by a rotary atomizer) or milledproduct as indicated above can optionally be subjected to anagglomeration stage, which consists, for example, of a directcompression, a wet granulation (that is to say, with use of a binder,such as water, silica suspension, and the like), an extrusion or,preferably, a dry compacting. When the latter technique is employed, itcan prove to be opportune, before carrying out the compacting, todeaerate (operation also referred to as predensifying or degassing) thepulverulent products so as to remove the air included in the latter andto provide more uniform compacting.

The precipitated silica capable of then being obtained by thisagglomeration stage generally exists in the form of granules.

The invention also relates to the precipitated silicas obtained orcapable of being obtained by the process according to the invention.

In general, these precipitated silicas exhibit, at their surface,molecules of the polycarboxylic acid employed and/or of carboxylatecorresponding to the polycarboxylic acid employed.

An additional subject matter of the present invention is a precipitatedsilica with the specific characteristics, which can be used inparticular as alternative filler for polymer compositions,advantageously providing them with a reduction in their viscosity and animprovement in their dynamic properties, while retaining theirmechanical properties.

In the account which follows, the BET specific surface is determinedaccording to the Brunauer-Emmett-Teller method described in The Journalof the American Chemical Society, Vol. 60, page 309, February 1938, andcorresponding to the standard NF ISO 5794-1, Appendix D (June 2010). TheCTAB specific surface is the external surface, which can be determinedaccording to the standard NF ISO 5794-1, Appendix G (June 2010).

The content of polycarboxylic acid+corresponding carboxylate denoted(C), expressed as total carbon, can be measured using a carbon/sulfuranalyzer, such as the Horiba EMIA 320 V2. The principle of thecarbon/sulfur analyzer is based on the combustion of a solid sample in astream of oxygen in an induction furnace (adjusted to approximately 170mA) and in the presence of combustion accelerators (approximately 2grams of tungsten (in particular Lecocel 763-266) and approximately 1gram of iron). The analysis lasts approximately 1 minute.

The carbon present in the sample to be analyzed (weight of approximately0.2 gram) combines with the oxygen to form CO₂, CO. These decompressiongases are subsequently analyzed by an infrared detector.

The moisture from the sample and the water produced during theseoxidation reactions is removed by passing over a cartridge comprising adehydrating agent (magnesium perchlorate) in order not to interfere withthe infrared measurement.

The result is expressed as percentage by weight of element carbon.

The content of aluminum, denoted (Al), can be determined by wavelengthdispersive X-ray fluorescence, for example with a Panalytical 2400spectrometer or, preferably, with a Panalytical MagixPro PW2540spectrometer. The principal of the method of measurement by X-rayfluorescence is as follows:

grinding of the silica is necessary when it is provided in the form ofsubstantially spherical beads (microbeads) or of granules, until ahomogeneous powder is obtained. The grinding can be carried out with anagate mortar (grinding 15 grams of silica approximately for a time of 2minutes) or any type of grinder not comprising aluminum,

the powder is analyzed as is in a vessel having a diameter of 40 mm witha polypropylene film with a thickness of 6 μm, under a heliumatmosphere, at an irradiation diameter of 37 mm, and the amount ofsilica analyzed is 9 cm³. The measurement of the aluminum content, whichrequires at most 5 minutes, is obtained from the Kα line (2θangle=145°,PE002 crystal, 550 μm collimator, gas flow detector, rhodium tube, 32 kVand 125 mA). The intensity of this line is proportional to the aluminumcontent. It is possible to employ a precalibration carried out usinganother measurement method, such as ICP-AES (Inductively CoupledPlasma—Atomic Emission Spectroscopy).

The aluminum content can also be measured by any other suitable method,for example by ICP-AES after dissolving in water in the presence ofhydrofluoric acid.

The presence of polycarboxylic acid(s) in the acid form and/or in thecarboxylate form can be established by surface infrared or diamond-ATR(Attenuated Total Reflection) Infrared.

The surface infrared analysis (by transmission) is carried out on aBruker Equinox 55 spectrometer on a pellet of pure product. The pelletis obtained after grinding the silica as is in an agate mortar andpelleting at 2 T/cm² for 10 seconds. The diameter of the pellet is 17mm. The weight of the pellet is between 10 and 20 mg. The pellet thusobtained is placed in the high vacuum chamber (10⁻⁷ mbar) of thespectrometer for one hour at ambient temperature before the analysis bytransmission. Acquisition takes place under high vacuum (acquisitionconditions: from 400 cm⁻¹ to 6000 cm⁻¹; number of scans: 100;resolution: 2 cm⁻¹).

The diamond-ATR analysis, carried out on a Bruker Tensor 27spectrometer, consists in depositing, on the diamond, a spatula tip ofsilica preground in an agate mortar and in then exerting a pressure. Theinfrared spectrum is recorded on the spectrometer in 20 scans, from 650cm⁻¹ to 4000 cm⁻¹. The resolution is 4 cm⁻¹.

The ratio denoted (R) is determined by the following relationship:

${(R) = {N \times \frac{\lbrack {( {100 \times {C/C_{Theo}}} ) \times M_{Al}} \rbrack}{( {{Al} \times M_{Ac}} )}}},$in which:

N is the number of carboxylic functional groups of the polycarboxylicacid (for example, N is equal to 2 in the case of succinic acid),

(C) and (Al) are the contents as defined above,

C_(T) is the carbon content of the polycarboxylic acid,

M_(Al) is the molecular weight of aluminum,

M_(Ac) is the molecular weight of the polycarboxylic acid.

The dispersive component of the surface energy γ_(s) ^(d) is determinedby inverse gas chromatography. Grinding of the silica is generallynecessary when it is provided in the form of granules, followed bysieving, for example at 106 μm-250 μm.

The technique used to calculate the dispersive component of the surfaceenergy γ_(s) ^(d) is Inverse Gas Chromatography at Infinite Dilution(IGC-ID) at 110° C. using a series of alkanes (normal alkanes) rangingfrom 6 to 10 carbon atoms, a technique based on gas chromatography butwhere the roles of the mobile phase and of the stationary phase(packing) are reversed. In this instance, the stationary phase in thecolumn is replaced by the (solid) material to be analyzed, in thisinstance the precipitated silica. With regard to the mobile phase, itconsists of the carrier gas (helium) and of the “probe” molecules chosenas a function of their interaction capability. The measurements aresuccessively carried out with each probe molecule. For each measurement,each probe molecule is injected into the column, in a very small amount(infinite dilution), as a mixture with methane. The methane is used todetermine the t0, the dead time of the column.

The subtraction of this dead time t0 from the retention time of theinjected probe results in the net retention time (t_(N)) of the latter.

These operating conditions, specific to the infinite dilution, mean thatthese retention times reflect solely the interactivity of the samplewith regard to these molecules. Physically, t_(N) corresponds to themean time which the probe molecule has spent in contact with thestationary phase (the solid analyzed). For each probe molecule injected,three net retention times t_(N) are measured. The mean value and thecorresponding standard deviation are used to determine the specificretention volumes) (V_(g) ⁰) on the basis of the following relationship(formula [1]).

$\begin{matrix}{V_{g}^{0} = {\frac{D_{c}t_{N}}{M_{S}} \times \frac{273.15}{T}}} & {{formula}\mspace{14mu}\lbrack 1\rbrack}\end{matrix}$

The latter corresponds to the volume of carrier gas (brought back to 0°C.) necessary to elute the probe molecule per 1 gram of stationary phase(solid examined). This standard quantity makes it possible to comparethe results, whatever the flow rate of carrier gas and the weight ofstationary phase used. The formula [1] involves: M_(s) the weight ofsolid in the column, D_(c) the flow rate of carrier gas and T themeasurement temperature.

The specific retention volume is subsequently used to access ΔG_(a), thevariation in free enthalpy of adsorption of the probe, according to theformula [2], with R the universal ideal gas constant (R=8.314J·K⁻¹·mol⁻¹), on the solid present in the column.ΔG _(a) =RT·Ln(V _(g) ⁰)  formula [2]

This quantity ΔG_(a) is the starting point for the determination of thedispersive component of the surface energy (γ_(s) ^(d)). The latter isobtained by plotting the straight line representing the variation infree enthalpy of absorption (ΔG_(a)) as a function of the carbon numbern_(c) of the n-alkane probes, as shown in the table below.

n-Alkane probes n_(c) n-hexane 6 n-heptane 7 n-octane 8 n-nonane 9n-decane 10

It is then possible to determine the dispersive component of the surfaceenergy γ_(s) ^(d) from the slope ΔG_(a) ^(CH2) of the straight line ofthe normal alkanes, corresponding to the free enthalpy of adsorption ofthe methylene group, obtained for a measurement temperature of 110° C.

The dispersive component of the surface energy γ_(s) ^(d) is thenrelated to the free enthalpy of adsorption ΔG_(a) ^(CH2) of themethylene group (Dorris and Gray method, J. Colloid Interface Sci., 77(180), 353-362) by the following relationship:

$\gamma_{s}^{d} = \frac{( {\Delta\; G_{a}^{{CH}_{2}}} )^{2}}{4{N_{A}^{2} \cdot a_{{CH}_{2}}^{2} \cdot \gamma_{{CH}_{2}}}}$with N_(A) being Avogadro's number (6.02×10²³ mol⁻¹), a_(CH) ₂ the areaoccupied by an adsorbed methylene group (0.06 nm²) and γ_(CH) ₂ thesurface energy of a solid consisting solely of methylene group anddetermined on polyethylene (35.6 mJ/m² at 20° C.).

The coordination number of the aluminum is determined by solid aluminumNMR.

The technique used to measure the water uptake consists generally inplacing the predried silica sample under given relative humidityconditions for a predetermined time; the silica then hydrates, whichcauses the weight of the sample to change from an initial value w (inthe dried state) to a final value w+dw. “Water uptake” of a silicaspecifically denotes, in particular throughout the continuation of theaccount, the dw/w ratio (that is to say, the weight of waterincorporated in the sample with respect to the weight of the sample inthe dry state), expressed as percentage, calculated for a silica samplesubjected to the following conditions during the measurement method:

preliminary drying: 8 hours, at 150° C.;

hydration: 24 hours, at 20° C., and under a relative humidity of 70%.

The experimental protocol employed consists in successively:

precisely weighing approximately 2 grams of the silica to be tested;

drying, for 8 hours, the silica thus weighed out in an oven adjusted toa temperature of 105° C.;

determining the weight w of the silica obtained on conclusion of thisdrying operation;

placing, for 24 hours, at 20° C., the dried silica in a closedcontainer, such as a desiccator, comprising a water/glycerol mixture, sothat the relative humidity of the closed medium is 70%;

determining the weight (w+dw) of the silica obtained subsequent to thistreatment at 70% relative humidity for 24 hours, the measurement of thisweight being carried out immediately after having removed the silicafrom the desiccator, so as to prevent variation in the weight of thesilica under the influence of the change in hygrometry between themedium at 70% relative humidity and the atmosphere of the laboratory.

The pore volumes and pore diameters are measured by mercury (Hg)porosimetry using a Micromeritics Autopore 9520 porosimeter and arecalculated by the Washburn relationship with a contact angle theta equalto 130° and a surface tension gamma equal to 484 dynes/cm (standard DIN66133). The preparation of each sample is carried out as follows: eachsample is predried in an oven at 200° C. for 2 hours.

The ability of the silicas to disperse and to deagglomerate can bequantified by means of the specific deagglomeration test below.

A particle size measurement is carried out (by laser diffraction) on asuspension of silica deagglomerated beforehand by ultrasonication; theability of the silica to deagglomerate (cleavage of the objects from 0.1to several tens of microns) is thus measured. The deagglomeration underultrasound is carried out using a Vibracell Bioblock (600 W) sonicatorequipped with a probe having a diameter of 19 mm. The particle sizemeasurement is carried out by laser diffraction on a Sympatec Helios/BFparticle sizer (equipped with an optical lens of R3 (0.9-175 μm) type),employing the Fraunhofer theory.

2 grams (+/−0.1 gram) of silica are introduced into a 50 ml beaker(height: 7.5 cm and diameter: 4.5 cm) and the weight is made up to 50grams by addition of 48 grams (+/−0.1 gram) of deionized water. A 4%aqueous silica suspension is thus obtained.

The deagglomeration under ultrasound is subsequently carried out asfollows: the “TIMER” button of the sonicator is pressed and the time isadjusted to 5 minutes 30 seconds. The amplitude of the probe(corresponding to the nominal power) is adjusted to 80% and then theultrasound probe is immersed over 5 centimeters in the silica suspensionpresent in the beaker. The ultrasound probe is then switched on and thedeagglomeration is carried out for 5 minutes 30 seconds at 80% amplitudeof the probe.

The particle size measurement is subsequently carried out byintroducing, into the vessel of the particle sizer, a volume V(expressed in ml) of the suspension, this volume V being such that 8%optical density is achieved on the particle sizer.

The median diameter Ø₅₀, after deagglomeration with ultrasound, is suchthat 50% of the particles by volume have a size of less than Ø₅₀ and 50%have a size of greater than Ø₅₀. The value of the median diameter Ø₅₀which is obtained decreases in proportion as the ability of the silicato deagglomerate increases.

It is also possible to determine the ratio (10×V/optical density of thesuspension detected by the particle sizer), this optical densitycorresponding to the true value detected by the particle sizer duringthe introduction of the silica.

This ratio (deagglomeration factor F_(D)) is indicative of the contentof particles with a size of less than 0.1 μm which are not detected bythe particle sizer. This ratio increases in proportion as the ability ofthe silica to deagglomerate increases.

The pH is measured according to the following method deriving from thestandard ISO 787/9 (pH of a 5% suspension in water):

Equipment:

calibrated pH meter (accuracy of reading to 1/100^(th))

combined glass electrode

200 ml beaker

100 ml measuring cylinder

balance accurate to within about 0.01 g.

Procedure:

5 grams of silica are weighed to within about 0.01 gram into the 200 mlbeaker. 95 ml of water, measured from the graduated measuring cylinder,are subsequently added to the silica powder. The suspension thusobtained is vigorously stirred (magnetic stirring) for 10 minutes. ThepH measurement is then carried out.

The precipitated silica according to the invention is characterized inthat it has:

a BET specific surface of between 45 and 550 m²/g, in particular between70 and 370 m²/g, especially between 80 and 300 m²/g,

a content (C) of polycarboxylic acid+corresponding carboxylate,expressed as total carbon, of at least 0.15% by weight, in particular ofat least 0.20% by weight,

an aluminum (Al) content of at least 0.20% by weight, in particular ofat least 0.25% by weight.

The precipitated silica according to the invention can in particularexhibit a BET specific surface of between 100 and 240 m²/g, inparticular between 120 and 190 m²/g, for example between 130 and 170m²/g.

The precipitated silica according to the invention can in particularexhibit a content (C) of polycarboxylic acid+corresponding carboxylate,expressed as total carbon, of at least 0.25% by weight, in particular ofat least 0.30% by weight, for example of at least 0.35% by weight,indeed even of at least 0.45% by weight.

The precipitated silica in accordance with the invention can inparticular exhibit an aluminum (Al) content of at least 0.30% by weight,in particular of at least 0.33% by weight. It generally exhibits analuminum (Al) content of less than 1% by weight, in particular of atmost 0.50% by weight, for example of at most 0.45% by weight.

The presence of the polycarboxylic acids and/or of the carboxylatescorresponding to the polycarboxylic acids at the surface of the silicaaccording to the invention can be illustrated by the presence ofshoulders characteristic of the C—O and C═O bonds, visible on theinfrared spectra, obtained in particular by surface (transmission)infrared or diamond-ATR infrared (in particular between 1540 and 1590cm⁻¹ and between 1380 and 1420 cm⁻¹ for C—O, and between 1700 and 1750cm⁻¹ for C═O).

In general, the precipitated silica according to the invention exhibits,at its surface, molecules of an abovementioned polycarboxylic acidand/or of carboxylate corresponding to an abovementioned polycarboxylicacid.

For example, it can exhibit, at its surface, molecules of succinic acidin the acid form and/or in the carboxylate form.

In general, the precipitated silica according to the invention has aCTAB specific surface of between 40 and 525 m²/g, in particular between70 and 350 m²/g, especially between 80 and 310 m²/g, for example between100 and 240 m²/g. It can in particular be between 130 and 200 m²/g, forexample between 140 and 190 m²/g.

In general, the precipitated silica according to the invention exhibitsa BET specific surface/CTAB specific surface ratio of between 0.9 and1.2, that is to say that it exhibits a low microporosity.

Preferably, the precipitated silica according to the invention has aratio (R) between 0.4 and 3.5, in particular between 0.4 and 2.5. Thisratio (R) can also be between 0.5 and 3.5, in particular between 0.5 and2.5, especially between 0.5 and 2, for example between 0.8 and 2, indeedeven between 0.8 and 1.8, or between 0.8 and 1.6.

Preferably, the precipitated silica according to the invention exhibitsa dispersive component of the surface energy γ_(s) ^(d) of less than 43mJ/m², in particular of less than 42 mJ/m².

It can exhibit a dispersive component of the surface energy γ_(s) ^(d)of at least 40 mJ/m² and of less than 43 mJ/m², in particular ofstrictly between 40 and 43 mJ/m², for example of strictly between 40 and42 mJ/m².

Preferably, it exhibits a dispersive component of the surface energyγ_(s) ^(d) of less than 40 mJ/m², in particular of less than 35 mJ/m².

The precipitated silica according to the invention can have a specificdistribution of the coordination number of the aluminum, determined bysolid aluminum NMR. In general, at most 85% by number, in particular atmost 80% by number, in particular between 70% and 85% by number, forexample between 70% and 80% by number, of the aluminum atoms of thesilica according to the invention can exhibit a tetrahedral coordinationnumber, that is to say, can be in a tetrahedral site. In particular,between 15% and 30% by number, for example between 20% and 30% bynumber, of the aluminum atoms of the silica according to the inventioncan exhibit a pentahedral or octahedral coordination number, that is tosay, can be in a pentahedral or octahedral site.

The precipitated silica according to the invention can exhibit a wateruptake of greater than 6%, in particular of greater than 7%, especiallyof greater than 7.5%, for example of greater than 8%, indeed even ofgreater than 8.5%.

In general, the precipitated silica according to the invention exhibitsa high ability to disperse (in particular in elastomers) and todeagglomerate.

The precipitated silica according to the invention can exhibit adiameter Ø₅₀, after deagglomeration with ultrasound, of at most 5 μm,preferably of at most 4 μm, in particular of between 3.5 and 2.5 μm.

The precipitated silica according to the invention can exhibit anultrasound deagglomeration factor F_(D) of greater than 5.5 ml, inparticular of greater than 7.5 ml, for example of greater than 12 ml.

Another parameter of the precipitated silica according to the inventioncan lie in the distribution of its pore volume and in particular in thedistribution of the pore volume which is generated by the pores havingdiameters of less than or equal to 400 Å. The latter volume correspondsto the useful pore volume of the fillers employed in the reinforcementof elastomers. In general, the analysis of the programs shows that thissilica, equally well in the form of substantially spherical beads(microbeads), of powder or of granules, preferably has a poredistribution such that the pore volume generated by the pores having adiameter of between 175 and 275 Å (V2) represents at least 50%, inparticular at least 55%, especially between 55% and 65%, for examplebetween 55% and 60%, of the pore volume generated by the pores withdiameters of less than or equal to 400 Å (V1). When the precipitatedsilica according to the invention is provided in the form of granules,it can optionally have a pore distribution such that the pore volumegenerated by the pores having a diameter of between 175 and 275 Å (V2)represents at least 60% of the pore volume generated by the pores withdiameters of less than or equal to 400 Å (V1).

The precipitated silica according to the invention preferably exhibits apH of between 3.5 and 7.5, more preferably still between 4 and 7, inparticular between 4.5 and 6.

The precipitated silica according to the invention can be provided inany physical state, that is to say that it can be provided in the formof substantially spherical beads (microbeads), of a powder or ofgranules.

It can thus be provided in the form of substantially spherical beadswith a mean size of at least 80 μm, preferably of at least 150 μm, inparticular of between 150 and 270 μm; this mean size is determinedaccording to the standard NF X 11507 (December 1970) by dry sieving anddetermination of the diameter corresponding to a cumulative oversize of50%.

It can also be provided in the form of a powder with a mean size of atleast 3 μm, in particular of at least 10 μm, preferably of at least 15μm.

It can be provided in the form of granules (generally of substantiallyparallelepipedal shape) with a size of at least 1 mm, for example ofbetween 1 and 10 mm, in particular along the axis of their greatestdimension.

The silica according to the invention is preferably obtained by theprocess described above, in particular the specific preparation process.

Advantageously, the precipitated silicas according to the presentinvention or (capable of being) obtained by the process according to theinvention described above confer, on the polymeric (elastomeric)compositions into which they are introduced, a highly satisfactorycompromise in properties, in particular a reduction in the viscosity andpreferably an improvement in their dynamic properties, while retainingtheir mechanical properties. They thus advantageously make possible animprovement in the processing/reinforcement/hysteresis propertiescompromise. Preferably, they exhibit a good ability to disperse and todeagglomerate in polymeric (elastomeric) compositions.

The precipitated silicas according to the present invention or (capableof being) obtained by the process described above according to theinvention can be used in numerous applications.

They can be employed, for example, as catalyst support, as absorbent foractive materials (in particular support for liquids, especially used infood, such as vitamins (vitamin E) or choline chloride), in polymer,especially elastomer, or silicone compositions, as viscosifying,texturizing or anticaking agent, as battery separator component, or asadditive for toothpaste, concrete or paper.

However, they find a particularly advantageous application in thereinforcement of natural or synthetic polymers.

The polymer compositions in which they can be employed, in particular asreinforcing filler, are generally based on one or more polymers orcopolymers (especially bipolymers or terpolymers), in particular on oneor more elastomers, preferably exhibiting at least one glass transitiontemperature of between −150° C. and +300° C., for example between −150°C. and +20° C.

Mention may in particular be made, as possible polymers, of dienepolymers, in particular diene elastomers.

For example, use may be made of polymers or copolymers (in particularbipolymers or terpolymers) deriving from aliphatic or aromatic monomers,comprising at least one unsaturation (such as, in particular, ethylene,propylene, butadiene, isoprene, styrene, acrylonitrile, isobutylene orvinyl acetate), polybutyl acrylate, or their mixtures; mention may alsobe made of silicone elastomers, functionalized elastomers, for examplefunctionalized by chemical groups positioned along the macromolecularchain and/or at one or more of its ends (for example by functionalgroups capable of reacting with the surface of the silica), andhalogenated polymers. Mention may be made of polyamides.

The polymer (copolymer) can be a bulk polymer (copolymer), a polymer(copolymer) latex or else a solution of polymer (copolymer) in water orin any other appropriate dispersing liquid.

Mention may be made, as diene elastomers, for example, of polybutadienes(BRs), polyisoprenes (IRs), butadiene copolymers, isoprene copolymers,or their mixtures, and in particular styrene/butadiene copolymers (SBRs,in particular ESBRs (emulsion) or SSBRs (solution)), isoprene/butadienecopolymers (BIRs), isoprene/styrene copolymers (SIRs),isoprene/butadiene/styrene copolymers (SBIRs), ethylene/propylene/dieneterpolymers (EPDMs), and also the associated functionalized polymers(exhibiting, for example, pendant polar groups or polar groups at thechain end, which can interact with the silica).

Mention may also be made of natural rubber (NR) and epoxidized naturalrubber (ENR).

The polymer compositions can be vulcanized with sulfur (vulcanisates arethen obtained) or crosslinked, in particular with peroxides or othercrosslinking systems (for example diamines or phenolic resins).

In general, the polymer compositions additionally comprise at least one(silica/polymer) coupling agent and/or at least one covering agent; theycan also comprise, inter alia, an antioxidant.

Use may in particular be made, as coupling agents, as nonlimitingexamples, of “symmetrical” or “unsymmetrical” silane polysulfides;mention may more particularly be made ofbis((C₁-C₄)alkoxyl(C₁-C₄)alkylsilyl(C₁-C₄)alkyl) polysulfides (inparticular disulfides, trisulfides or tetrasulfides), such as, forexample, bis(3-(trimethoxysilyl)propyl)polysulfides orbis(3-(triethoxysilyl)propyl)polysulfides, such as triethoxysilylpropyltetrasulfide. Mention may also be made of monoethoxydimethylsilylpropyltetrasulfide. Mention may also be made of silanes comprising masked orfree thiol functional groups.

The coupling agent can be grafted beforehand to the polymer. It can alsobe employed in the free state (that is to say, not grafted beforehand)or grafted at the surface of the silica. It is the same for the optionalcovering agent.

The coupling agent can optionally be combined with an appropriate“coupling activator”, that is to say a compound which, mixed with thiscoupling agent, increases the effectiveness of the latter.

The proportion by weight of silica in the polymer composition can varywithin a fairly wide range. It normally represents from 10% to 200%, inparticular from 20% to 150%, especially from 20% to 80% (for examplefrom 30% to 70%) or from 80% to 120% (for example from 90% to 110%), ofthe amount of the polymer(s).

The silica according to the invention can advantageously constitute allof the reinforcing inorganic filler and even all of the reinforcingfiller of the polymer composition.

However, this silica according to the invention can optionally becombined with at least one other reinforcing filler, such as, inparticular, a commercial highly dispersible silica, such as, forexample, Z1165MP or Z1115MP, a treated precipitated silica (for example,a precipitated silica “doped” using a cation, such as aluminum); anotherreinforcing inorganic filler, such as, for example, alumina, indeed evena reinforcing organic filler, in particular carbon black (optionallycovered with an inorganic layer, for example of silica). The silicaaccording to the invention then preferably constitutes at least 50% byweight, indeed even at least 80% by weight, of all of the reinforcingfiller.

Mention may be made, as nonlimiting examples of finished articlescomprising at least one of (in particular based on) said polymercompositions described above (in particular based on the abovementionedvulcanisates), of footwear soles (preferably in the presence of a(silica/polymer) coupling agent, for example triethoxysilylpropyltetrasulfide), floor coverings, gas barriers, flame-retardant materialsand also engineering components, such as rollers for cableways, sealsfor domestic electrical appliances, seals for liquid or gas pipes,braking system seals, pipes (flexible), sheathings (in particular cablesheathings), cables, engine supports, battery separators, conveyorbelts, transmission belts or, preferably, tires, in particular tiretreads (especially for light vehicles or for heavy-goods vehicles (forexample trucks)).

The following examples illustrate the invention without, however,limiting the scope thereof.

EXAMPLES Example 1

The suspension of precipitated silica used is a silica slurry obtainedon conclusion of the precipitation reaction during the process for thepreparation of the Z1165MP silica.

The silica suspension (1396 liters) is filtered and washed on a filterpress and is then subjected to compacting at a pressure of 5.5 bar onthe same filter. The silica cake which results therefrom exhibits asolids content of 23% by weight.

Prior to the liquefaction operation, a 100 g/l solution of succinic acidis prepared by dissolving the succinic acid in water (35° C.) withstirring.

The cake obtained in the filtration stage is subjected to a liquefactionoperation in a continuous vigorously stirred reactor (for approximately3 hours) with 2270 grams of the sodium aluminate solution (Al/SiO₂ ratioby weight of 0.33%).

Once the liquefaction has been carried out, 9670 grams of the succinicacid solution prepared beforehand are added to a portion (303 liters) ofthe disintegrated cake (succinic acid/SiO₂ ratio by weight of 1.15%).

This treated portion (having a solids content of 22% by weight) of thedisintegrated cake is subsequently dried using a nozzle atomizer byspraying the disintegrated cake through a 1.5 mm nozzle with a pressureof 25 bar for 50 minutes under the following mean conditions of flowrate and of temperatures:

Mean inlet temperature: 535° C.

Mean outlet temperature: 155° C.

Mean flow rate: 202 l/h.

The characteristics of the silica S1 obtained (in the form ofsubstantially spherical beads) are then the following:

BET (m²/g) 147 Content of polycarboxylic acid + carboxylate (C) (%) 0.35Aluminum (Al) content (%) 0.30 Ratio (R) 1.3 CTAB (m²/g) 151 Y_(s) ^(d)(mJ/m²) 33.2 Water uptake (%) 8.5 Ø₅₀ (μm) after deagglomeration withultrasound 2.7 Fd after deagglomeration with ultrasound 18.9 V2/V1 (%)56 pH 5.2

Example 2 (Comparative)

The suspension of precipitated silica used is a silica cake (having asolid content of 23% by weight) obtained on conclusion of the filtrationstage during the process for the preparation of the Z1165MP silica.

Prior to the liquefaction operation, a 100 g/l maleic acid solution isprepared by dissolving maleic acid in water (at 35° C.) with stirring.

The cake obtained in the filtration stage is subjected to a liquefactionoperation in a continuous vigorously stirred reactor (for approximately90 minutes) with addition to the cake of 4400 grams of the 100 g/lmaleic acid solution (maleic acid/SiO₂ ratio by weight of 1.0%).

This disintegrated cake (having a solids content of 22% by weight) issubsequently dried using a nozzle atomizer by spraying the disintegratedcake through a 1.5 mm nozzle with a pressure of 25 bar under thefollowing mean conditions of flow rate and of temperatures:

Mean inlet temperature: 577° C.

Mean outlet temperature: 157° C.

Mean flow rate: 220 l/h.

The characteristics of the silica C1 obtained (in the form ofsubstantially spherical beads) are then the following:

BET (m²/g) 169 Content of polycarboxylic acid + carboxylate (C) (%) 0.19Aluminum (Al) content (%) <0.05 Ratio (R) >4.3 CTAB (m²/g) 178 Y_(s)^(d) (mJ/m²) 51 Ø₅₀ (μm) after deagglomeration with ultrasound 3.6 Fdafter deagglomeration with ultrasound 19.3 V2/V1 (%) 58 pH 3.8

Example 3

The elastomeric compositions, the make up of which, expressed as partsby weight per 100 parts of elastomers (phr), is shown in table I below,are prepared in an internal mixer of Brabender type (380 ml):

TABLE I Composition Control 1 Composition 1 SBR (1) 103 103 BR (1) 25 25Silica 1 (2) 80 Silica S1 (3) 80 Coupling agent (4) 6.4 6.4 Carbon black(N330) 3.0 3.0 Plasticizer (5) 7 7 ZnO 2.5 2.5 Stearic acid 2 2Antioxidant (6) 1.9 1.9 DPG (7) 1.5 1.5 CBS (8) 2 2 Sulfur 1.1 1.1 (1)Solution SBR (Buna VSL5025-2 from Lanxess) with 50 +/− 4% of vinylunits; 25 +/− 2% of styrene units; Tg in the vicinity of −20° C.; 100phr of SBR extended with 37.5 +/− 2.8% by weight of oil/BR (Buna CB 25from Lanxess) (2) Silica Z1165 MP from Rhodia (3) Silica S1 according tothe present invention (liquefaction with addition of sodium aluminate,then addition of succinic acid after liquefaction (example 1 above)) (4)TESPT (Luvomaxx TESPT from Lehvoss France sarl) (5) Nytex 4700 fromNynas (6) N-(1,3-Dimethylbutyl)-N-phenyl-para-phenylenediamine(Santoflex 6-PPD from Flexsys) (7) Diphenylguanidine (Rhenogran DPG-80from RheinChemie) (8) N-Cyclohexyl-2-benzothiazolesulfenamide (RhenogranCBS-80 from RheinChemie)

The silica Z1165 MP exhibits the following characteristics:

BET (m²/g) 161 Content of polycarboxylic acid + carboxylate (C) (%) 0.00Aluminum (Al) content (%) 0.30 Ratio (R) 0 CTAB (m²/g) 155 Y_(s) ^(d)(mJ/m²) 48.7 Water uptake (%) 9.4

Process for the Preparation of the Elastomeric Compositions:

The process for the preparation of the rubber compositions is carriedout in two successive preparation phases. A first phase consists of aphase of high-temperature thermomechanical working. It is followed by asecond phase of mechanical working at temperatures of less than 110° C.This phase makes possible the introduction of the vulcanization system.

The first phase is carried out using a mixing device, of internal mixertype, of Brabender brand (capacity of 380 ml). The filling coefficientis 0.6. The initial temperature and the speed of the rotors are set oneach occasion so as to achieve mixture dropping temperatures ofapproximately 140-160° C.

Broken down here into two passes, the first phase makes it possible toincorporate, in a first pass, the elastomers and then the reinforcingfiller (introduction in installments) with the coupling agent and thestearic acid. For this pass, the duration is between 4 and 10 minutes.

After cooling the mixture (temperature of less than 100° C.), a secondpass makes it possible to incorporate the zinc oxide and the protectingagents/antioxidants (in particular 6-PPD). The duration of this pass isbetween 2 and 5 minutes.

After cooling the mixture (temperature of less than 100° C.), the secondphase makes possible the introduction of the vulcanization system(sulfur and accelerators, such as CBS). It is carried out on an openmill, preheated to 50° C. The duration of this phase is between 2 and 6minutes.

Each final mixture is subsequently calandered in the form of plaqueswith a thickness of 2-3 mm.

With regard to these “raw” mixtures obtained, an evaluation of theirrheological properties makes it possible to optimize the vulcanizationtime and the vulcanization temperature.

Subsequently, the mechanical and dynamic properties of the mixturesvulcanized at the curing optimum (T98) are measured.

Rheological Properties

Viscosity of the Raw Mixtures:

The Mooney consistency is measured on the compositions in the raw stateat 100° C. using an MV 2000 rheometer and also the determination of theMooney stress-relaxation rate according to the standard NF ISO 289.

The value of the torque, read at the end of 4 minutes after preheatingfor one minute (Mooney Large (1+4)—at 100° C.), is shown in table II.The test is carried out after preparing the raw mixtures and then afteraging for 3 weeks at a temperature of 23+/−3° C.

TABLE II Compositions Control 1 Composition 1 ML (1 + 4) − 100° C.Initial 79 74 Mooney relaxation Initial 0.312 0.343 ML (1 + 4) − 100° C.After 3 weeks 93 83 (23 +/− 3° C.) Mooney relaxation After 3 weeks 0.2580.307 (23 +/− 3° C.)

It is found that the silica S1 of the present invention (Composition 1)makes possible a sizeable reduction in the initial raw viscosity, withrespect to the value of the control mixture.

It is also found that the silica S1 of the present invention(Composition 1) makes it possible to retain the advantage in reduced rawviscosity, with respect to the value of the control mixture, after 3weeks of storage.

This type of behavior over time is of great use to a person skilled inthe art in the case of the processing of silica-comprising rubbermixtures.

Rheometry of the Compositions:

The measurements are carried out on the compositions in the raw state.The results relating to the rheology test, which is carried out at 160°C. using a Monsanto ODR rheometer according to the standard NF ISO 3417,have been given in table III.

According to this test, the test composition is placed in the testchamber regulated at the temperature of 160° C. for 30 minutes, and theresistive torque opposed by the composition to a low-amplitude (3°)oscillation of a biconical rotor included in the test chamber ismeasured, the composition completely filling the chamber underconsideration.

The following are determined from the curve of variation in the torqueas a function of time:

the minimum torque (Tmin), which reflects the viscosity of thecomposition at the temperature under consideration;

the maximum torque (Tmax);

the delta torque (ΔT=Tmax−Tmin), which reflects the degree ofcrosslinking brought about by the action of the crosslinking system and,if the need arises, of the coupling agents;

the time T98 necessary to obtain a vulcanization state corresponding to98% of complete vulcanization (this time is taken as vulcanizationoptimum);

and the scorch time TS2, corresponding to the time necessary in order tohave a rise of 2 points above the minimum torque at the temperatureunder consideration (160° C.) and which reflects the time during whichit is possible to process the raw mixtures at this temperature withouthaving initiation of vulcanization (the mixture cures from TS2).

The results obtained are shown in table III.

TABLE III Compositions Control 1 Composition 1 Tmin (dN · m) 17.0 15.7Tmax (dN · m) 56.0 61.9 Delta torque (dN · m) 39.0 46.2 TS2 (min) 5.86.2 T98 (min) 26.2 26.4

It is found that the composition resulting from the invention(Composition 1) exhibits a satisfactory combination of rheologicalproperties.

In particular, while having a reduced raw viscosity, it exhibits a lowerminimum torque value and a higher maximum torque value than those of thecontrol mixture, which reflects a greater processability of the preparedmixture.

The use of the silica S1 of the present invention (Composition 1) makesit possible to reduce the minimum viscosity (which is a sign of animprovement in the raw viscosity) with respect to the control mixturewithout damaging the vulcanization behavior.

Mechanical Properties of the Vulcanisates:

The measurements are carried out on the optimally vulcanizedcompositions (T98) for a temperature of 160° C.

Uniaxial tensile tests are carried out in accordance with theinstructions of the standard NF ISO 37 with test specimens of H2 type ata rate of 500 mm/min on an Instron 5564 device. The x % moduli,corresponding to the stress measured at x % of tensile strain, areexpressed in MPa. It is possible to determine a reinforcing index (RI)which is equal to the ratio of the modulus at 300% strain to the modulusat 100% strain.

The Shore A hardness measurement on the vulcanisates is carried outaccording to the instructions of the standard ASTM D 2240. The givenvalue is measured at 15 seconds.

The properties measured are collated in table IV.

TABLE IV Compositions Control 1 Composition 1 10% Modulus (MPa) 0.6 0.7100% Modulus (MPa) 2.1 2.4 300% Modulus (MPa) 11.6 13.4 RI 5.6 5.7 ShoreA hardness - 15 s (pts) 55 55

It is found that the composition resulting from the invention(Composition 1) exhibits a satisfactory compromise in mechanicalproperties, with respect to what is obtained with the controlcomposition 1.

Composition 1 thus exhibits relatively low 10% and 100% moduli and arelatively high 300% modulus, hence a good reinforcing index.

The use of a silica S1 of the present invention (Composition 1) makes itpossible to obtain a satisfactory level of reinforcement, with respectto the control mixture.

Dynamic Properties of the Vulcanisates:

The dynamic properties are measured on a viscosity analyser (MetravibVA3000) according to the standard ASTM D5992.

The values for loss factor (tan δ) and compressive dynamic complexmodulus (E*) are recorded on vulcanized samples (cylindrical testspecimen with a cross section of 95 mm² and a height of 14 mm). Thesample is subjected at the start to a 10% prestrain and then to asinusoidal strain in alternating compression of plus or minus 2%. Themeasurements are carried out at 60° C. and at a frequency of 10 Hz.

The results, presented in table V, are the compressive complex modulus(E*, 60° C., 10 Hz) and the loss factor (tan δ, 60° C., 10 Hz).

The values for the loss factor (tan δ) and for amplitude of dynamicshear elastic modulus (ΔG′) are recorded on vulcanized samples(parallelepipedal test specimen with a cross section of 8 mm² and aheight of 7 mm). The sample is subjected to a double alternatingsinusoidal shear strain at a temperature of 40° C. and at a frequency of10 Hz. The strain amplitude sweeping processes are carried out accordingto an outward-return cycle, proceeding outward from 0.1% to 50% and thenreturning from 50% to 0.1%.

The results, presented in table V, result from the return strainamplitude sweep and relate to the maximum value of the loss factor (tanδ max return, 40° C., 10 Hz) and to the amplitude of the elastic modulus(ΔG′, 40° C., 10 Hz) between the values at 0.1% and 50% strain (Payneeffect).

TABLE V References Control 1 Composition 1 E*, 60° C., 10 Hz (MPa) 5.85.5 Tan δ, 60° C., 10 Hz 0.125 0.117 ΔG′ , 40° C., 10 Hz (MPa) 1.4 1.2Tan δ max return, 40° C., 10 Hz 0.190 0.179

The use of a silica S1 of the present invention (Composition 1) makes itpossible to improve the maximum value of the loss factor and theamplitude of the elastic modulus or Payne effect, with respect to thecontrol mixture.

The examination of the various tables II to V shows that the compositionin accordance with the invention (Composition 1) makes it possible toobtain a good processing/reinforcement/hysteresis properties compromise,with respect to the control mixture, and in particular a sizeable gainin raw viscosity which remains stable on storage over time.

Example 4

The elastomeric compositions, the make up of which, expressed as partsby weight per 100 parts of elastomers (phr), is shown in table VI below,are prepared in an internal mixer of Brabender type (380 ml):

TABLE VI Composition Control 2 Control 3 Composition 2 NR (1) 100 100100 Silica 1 (2) 55 Silica C1 (3) 55 Silica S1 (4) 55 Coupling agent (5)4.4 4.4 4.4 ZnO 3 3 3 Stearic acid 2.5 2.5 2.5 Antioxidant 1 (6) 1.5 1.51.5 Antioxidant 2 (7) 1.0 1.0 1.0 Carbon black (N330) 3.0 3.0 3.0 CBS(8) 1.7 1.7 1.7 Sulfur 1.5 1.5 1.5 (1) Natural rubber CVR CV60 (suppliedby Safic-Alcan) (2) Silica Z1165 MP from Rhodia (3) Silica C1(liquefaction with addition of maleic acid (example 4, comparative)) (4)Silica S1 according to the present invention (liquefaction with additionof sodium aluminate, then addition of succinic acid after liquefaction(example 1 above)) (5) TESPT (Luvomaxx TESPT from Lehvoss France sarl)(6) N-(1,3-Dimethylbutyl)-N-phenyl-para-phenylenediamine (Santoflex6-PPD from Flexsys) (7) 2,2,4-Trimethyl-1H-quinoline (Permanax TQ fromFlexsys) (8) N-Cyclohexyl-2-benzothiazolesulfenamide (Rhenogran CBS-80from RheinChemie)

Process for the Preparation of the Elastomeric Compositions:

The process for the preparation of the rubber compositions is carriedout in two successive preparation phases. A first phase consists of aphase of high-temperature thermomechanical working. It is followed by asecond phase of mechanical working at temperatures of less than 110° C.This phase makes possible the introduction of the vulcanization system.

The first phase is carried out using a mixing device, of internal mixertype, of Brabender brand (capacity of 380 ml). The filling coefficientis 0.6. The initial temperature and the speed of the rotors are set oneach occasion so as to achieve mixture dropping temperatures ofapproximately 140-160° C.

Broken down here into two passes, the first phase makes it possible toincorporate, in a first pass, the elastomers and then the reinforcingfiller (introduction in installments) with the coupling agent and thestearic acid. For this pass, the duration is between 4 and 10 minutes.

After cooling the mixture (temperature of less than 100° C.), a secondpass makes it possible to incorporate the zinc oxide and the protectingagents/antioxidants (in particular 6-PPD). For this pass, the durationis between 2 and 5 minutes.

After cooling the mixture (temperature of less than 100° C.), the secondphase makes possible the introduction of the vulcanization system(sulfur and accelerators, such as CBS). It is carried out on an openmill, preheated to 50° C. The duration of this phase is between 2 and 6minutes.

The final composition is subsequently calandered in the form of plaqueswith a thickness of 2-3 mm.

With regard to these “raw” mixtures, an evaluation of their rheologicalproperties makes it possible to optimize the vulcanization time and thevulcanization temperature.

Subsequently, the mechanical and dynamic properties of the mixturesvulcanized at the curing optimum (T98) are measured.

Rheological Properties

Viscosity of the Raw Mixtures:

The Mooney consistency is measured on the compositions in the raw stateat 100° C. using an MV 2000 rheometer and also the determination of theMooney stress-relaxation rate according to the standard NF ISO 289.

The value of the torque, read at the end of 4 minutes after preheatingfor one minute (Mooney Large (1+4)—at 100° C.), is shown in table VII.The test is carried out after preparing the raw mixtures and then afteraging for 10 days at a temperature of 23+/−3° C.

TABLE VII Control Control Composition Compositions 2 3 2 ML (1 + 4) -100° C. Initial 59 56 53 Mooney relaxation Initial 0.392 0.385 0.395 ML(1+ 4) - 100° C. After 11 days 65 59 57 (23 +/− 3° C.) Mooney relaxationAfter 11 days 0.380 0.399 0.384 (23 +/−3° C.)

It is found that the silica S1 of the present invention (Composition 2)makes possible a reduction in the initial raw viscosity, with respect tothe control mixture 2 and the control mixture 3.

It is also found that the silica S1 of the present invention(Composition 2) comprising succinic acid shows an enhanced performancein terms of reduction in the raw viscosity, with respect to the controlmixture 2 and the control mixture 3.

It is also observed that the use of the silica S1 of the presentinvention (Composition 2) makes it possible to retain the advantage inreduced raw viscosity, with respect to the control mixture 2 and thecontrol mixture 3, after 11 days of storage.

This type of behaviour over time is of great use to a person skilled inthe art in the case of the processing of a silica-comprising rubbermixture.

Rheometry of the Compositions:

The measurements are carried out on the compositions in the raw state.The results relating to the rheology test, which is carried out at 150°C. using a Monsanto ODR rheometer according to the standard NF ISO 3417,have been given in table VIII.

According to this test, the test composition is placed in the testchamber regulated at the temperature of 150° C. for 30 minutes, and theresistive torque opposed by the composition to a low-amplitude (3°)oscillation of a biconical rotor included in the test chamber ismeasured, the composition completely filling the chamber underconsideration.

The following are determined from the curve of variation in the torqueas a function of time:

the minimum torque (Tmin), which reflects the viscosity of thecomposition at the temperature under consideration;

the maximum torque (Tmax);

the delta torque (ΔT=Tmax−Tmin), which reflects the degree ofcrosslinking brought about by the action of the crosslinking system and,if the need arises, of the coupling agents;

the time T98 necessary to obtain a vulcanization state corresponding to98% of complete vulcanization (this time is taken as vulcanizationoptimum).

The results obtained are shown in table VIII.

TABLE VIII Compositions Control 2 Control 3 Composition 2 Tmin (dN · m)13.6 13.5 11.8 Tmax (dN · m) 71.6 69.4 77.3 Delta torque (dN · m) 58 5666 T98 (min) 25.2 26.9 25.0

It is found that the composition resulting from the invention(Composition 2) exhibits a satisfactory combination of rheologicalproperties.

In particular, while having a reduced raw viscosity, it exhibits a lowerminimum torque value and a higher maximum torque value than those of thecontrol mixture 2 and the control mixture 3, which reflects a greaterprocessability of the prepared mixture.

The use of the silica S1 of the present invention (Composition 2) makesit possible to reduce the minimum viscosity (low minimum torque Tmin,which is a sign of an improvement in the raw viscosity) with respect tothe control mixture 2 and the control mixture 3 without damaging thevulcanization behavior.

Mechanical Properties of the Vulcanisates:

The measurements are carried out on the optimally vulcanizedcompositions (T98) for a temperature of 150° C.

Uniaxial tensile tests are carried out in accordance with theinstructions of the standard NF ISO 37 with test specimens of H2 type ata rate of 500 mm/min on an Instron 5564 device. The x % moduli,corresponding to the stress measured at x % of tensile strain, and theultimate strength are expressed in MPa; the elongation at break isexpressed in %.

The Shore A hardness measurement on the vulcanisates is carried outaccording to the instructions of the standard ASTM D 2240. The givenvalue is measured at 15 seconds.

The properties measured are collated in table IX.

TABLE IX Compositions Control 2 Control 3 Composition 2 10% Modulus(MPa) 0.6 0.5 0.6 300% Modulus (MPa) 12.3 12.6 14.0 Ultimate strength(MPa) 26.0 26.8 28.8 Elongation at break (%) 532 521 541 RI 4.9 5.2 4.7Shore A hardness - 15 s (pts) 59 55 60

It is found that the composition resulting from the invention(Composition 2) exhibits a satisfactory compromise in mechanicalproperties, with respect to what is obtained with the control mixture 2and with the control mixture 3. In particular, it exhibits a betterultimate strength and a higher elongation at break, with respect to thecontrol mixture 2 and the control mixture 3.

Composition 2 thus exhibits a relatively low 10% modulus and arelatively high 300% modulus.

The use of a silica S1 of the present invention (Composition 2) makes itpossible to obtain a good level of reinforcement.

Dynamic Properties of the Vulcanisates:

The dynamic properties are measured on a viscosity analyser (MetravibVA3000) according to the standard ASTM D5992.

The values for loss factor (tan δ) and compressive dynamic complexmodulus (E*) are recorded on vulcanized samples (cylindrical testspecimen with a cross section of 95 mm² and a height of 14 mm). Thesample is subjected at the start to a 10% prestrain and then to asinusoidal strain in alternating compression of plus or minus 2%. Themeasurements are carried out at 60° C. and at a frequency of 10 Hz.

The results, presented in table X, are the compressive complex modulus(E*, 60° C., 10 Hz) and the loss factor (tan δ, 60° C., 10 Hz).

The values for the loss factor (tan δ) are recorded on vulcanizedsamples (parallelepipedal test specimen with a cross section of 8 mm²and a height of 7 mm). The sample is subjected to a double alternatingsinusoidal shear strain at a temperature of 60° C. and at a frequency of10 Hz. The strain amplitude sweeping processes are carried out accordingto an outward-return cycle, proceeding outward from 0.1% to 50% and thenreturning from 50% to 0.1%.

The results, presented in table X, result from the return strainamplitude sweep and relate to the maximum value of the loss factor (tanδ max return, 60° C., 10 Hz).

TABLE X Compositions Control 2 Control 3 Composition 2 E*, 60° C., 10 Hz(MPa) 6.5 5.6 6.7 Tan δ , 60° C., 10 Hz 0.125 0.118 0.104 Tan δ maxreturn, 60° C., 10 Hz 0.138 0.135 0.128

The use of a silica S1 of the present invention (Composition 2) makes itpossible to improve the maximum value of the loss factor in dynamiccompression, just like the Tan δ max return loss factor, with respect tothe control mixture 2 and the control mixture 3.

The examination of the various tables VII to X shows that thecomposition in accordance with the invention (Composition 2) makes itpossible to obtain a good processing/reinforcement/hysteresis propertiescompromise at 60° C., with respect to the control mixture 2 and thecontrol mixture 3. The raw viscosity of the mixture comprising thesilica of the present invention changes very little on storage overtime.

The invention claimed is:
 1. A tire comprising a precipitated silicahaving: a BET specific surface of between 45 and 550 m²/g, a content (C)of polycarboxylic acid and corresponding carboxylate, expressed as totalcarbon, of at least 0.15% by weight, wherein the polycarboxylic acidcomprises succinic acid, and an aluminum (Al) content of at least 0.20%by weight, wherein the precipitated silica exhibits a dispersivecomponent of the surface energy γ_(s) ^(d) of at least 40 mJ/m² and ofless than 43 mJ/m².
 2. The tire as claimed in claim 1, wherein the BETspecific surface is between 100 and 240 m²/g.
 3. The tire as claimed inclaim 1, wherein the content (C) of polycarboxylic acid andcorresponding carboxylate, expressed as total carbon, is at least 0.25%by weight.
 4. The tire as claimed in claim 1, wherein the aluminum (Al)content is at least 0.30% by weight.
 5. The tire as claimed in claim 1,wherein the precipitated silica exhibits a dispersive component of thesurface energy γ_(s) ^(d) of less than 42 mJ/m².
 6. The tire as claimedin claim 1, wherein the precipitated silica exhibits a water uptake ofgreater than 6%.
 7. The tire as claimed in claim 1, wherein theprecipitated silica exhibits a ratio (R), defined by the followingformula:${(R) = {N \times \frac{\lbrack {( {100 \times {C/C_{Theo}}} ) \times M_{Al}} \rbrack}{( {{Al} \times M_{Ac}} )}}},$in which: N is the number of carboxylic functional groups of thepolycarboxylic acid, C_(T) is the carbon content of the polycarboxylicacid, M_(Al) is the molecular weight of aluminum, M_(Ac) is themolecular weight of the polycarboxylic acid, of between 0.4 and 3.5. 8.The tire as claimed in claim 7, wherein the ratio (R) exhibited by theprecipitated silica is between 0.5 and 2.5.